New oxorhenium(V) compound for catalyzed oxygen atom transfer from picoline N-oxide to triarylphosphines

The synthesis and characterization of a new oxorhenium(V) compound is reported; it is [MeReO(edt)(bpym)], 8, where edt = 1,2-ethanedithiolate and bpym = 2,2'-bipyrimidine. Compound 8 was characterized by NMR spectroscopy and single-crystal X-ray analysis. It exists as a six-coordinate Re(V) compound comparable to the previously known [MeReO(edt)(bpy)] and [MeReO(mtp)(bpy)]. Compound 8 catalyzes the oxygen-atom-transfer reaction PicO + PZ3 --> Pic + Z3PO, whereas the other two do not. The kinetics of this reaction with catalyst 8 follows the rate law -d[PicO]/dt = k[8][PicO]/(1 + c[PZ3]). With different phosphines, the rate law has the same k value, 4.17 L mol(-1) s(-1), but different c values. For tritolylphosphine, c = 67.5 L mol(-1) in benzene at 25 degrees C. A mechanism has been proposed to account for these findings. The data establish that an open coordination site on rhenium is necessary for oxygen-atom-transfer reactions.     

Kinetics and mechanisms of catalytic oxygen atom transfer with oxorhenium(V) oxazoline complexes

The rhenium(V) monooxo complexes (hoz)2Re(O)Cl (1) and [(hoz)2Re(O)(OH2)][OTf] (2) have been synthesized and fully characterized (hoz = 2-(2'-hydroxyphenyl)-2-oxazoline). A single-crystal X-ray structure of 2 has been solved: space group = P1, a = 13.61(2) A, b = 14.76(2) A, c = 11.871(14) A, alpha = 93.69(4) degrees, beta = 99.43(4) degrees, gamma = 108.44(4) degrees, Z = 4; the structure was refined to final residuals R = 0.0455 and Rw = 0.1055. 1 and 2 catalyze oxygen atom transfer from aryl sulfoxides to alkyl sulfides and oxygen-scrambling between sulfoxides to yield sulfone and sulfide. Superior catalytic activity has been observed for 2 due to the availability of a coordination site on the rhenium. The active form of the catalyst is a dioxo rhenium(VII) intermediate, [Re(O)2(hoz)2]+ (3). In the presence of sulfide, 3 is rapidly reduced to [Re(O)(hoz)2]+ with sulfoxide as the sole organic product. The transition state is very sensitive to electronic influences. A Hammett correlation plot with para-substituted thioanisole derivatives gave a reaction constant rho of -4.6 +/- 0.4, in agreement with an electrophilic oxygen transfer from rhenium. The catalytic reaction features inhibition by sulfides at high concentrations. The equilibrium constants for sulfide binding to complex 2 (cause of inhibition), K2 (L x mol(-1)), were determined for a few sulfides: Me2S (22 +/- 3), Et2S (14 +/- 2), and tBu2S (8 +/- 2). Thermodynamic data, obtained from equilibrium measurements in solution, show that the S=O bond in alkyl sulfoxides is stronger than in aryl sulfoxides. The Re=O bond strength in 3 was estimated to be about 20 kcal x mol(-1). The high activity and oxygen electrophilicity of complex 3 are discussed and related to analogous molybdenum systems.     

Kinetics and mechanism of oxygen atom transfer from methyl phenyl sulfoxide to triarylphosphines catalyzed by an oxorhenium(V) dimer

An oxorhenium(V) dimer, [PMeReO(mtp)](2), D, where mtpH(2) is 2-(mercaptomethyl)thiophenol, catalyzes oxygen atom transfer reaction from methyl phenyl sulfoxide to triarylphosphines. Kinetic studies in benzene-d(6) at 23 degrees C indicate that the reaction takes place through the formation of an adduct between D and sulfoxide. The equilibrium constants, K(DL), for adduct formation were determined by spectrophotometric titration, and the values of K(DL) for MeS(O)C(6)H(4)-4-R were obtained as 14.1(2), 5.7(1), and 2.1(1) for R = Me, H, and Br, respectively. Following sulfoxide binding, oxygen atom transfer occurs with either internal or external nucleophilic assistance. Because [MeReO(mtp)](2) is a much more reactive catalyst than its monomerized form, MeReO(mtp)PPh(3), loss of the active catalyst during the time course of the reaction must be taken into account as a part of the kinetic analysis. As it happens, sulfoxide catalyzes monomerization. Monomerization by triarylphosphines was also studied in the presence of sulfoxide, and a mechanism for that reaction was also proposed. Both the phosphine-assisted monomerization and the phosphine-assisted pathway for oxygen atom transfer involve transition states with ternary components, D, sulfoxide, and phosphine, which we suggest are structural isomers of one another.     

Kinetics and mechanism of rhenium-catalyzed oxygen atom transfer from pyridine N-oxides to phosphines

The oxygen atom transfer (OAT) reaction cited does not occur on its own in >10 h. Oxorhenium(V) compounds having the formula MeReO(dithiolate)PZ(3) catalyze the reaction; the catalyst most studied was MeReO(mtp)PPh(3), 1, where mtpH(2) = 2-(mercaptomethyl)thiophenol. The mechanism was studied by multiple techniques. Kinetics (initial-rate and full-time-course methods) established this rate law: v = k(c)[1][PyO](2)[PPh(3)](-1). Here and elsewhere PyO symbolizes the general case XC(5)H(4)NO and PicO that with X = 4-Me. For 4-picoline, k(c) = (1.50 +/- 0.05) x 10(4) L mol(-1) s(-1) in benzene at 25.0 degrees C; the inverse phosphine dependence signals the need for the removal of phosphine from the coordination sphere of rhenium prior to the rate-controlling step (RCS). The actual entry of PPh(3) into the cycle occurs in a fast step later in the catalytic cycle, after the RCS; its relative rate constants (k(4)) were evaluated with pairwise combinations of phosphines. Substituent effects were studied in three ways: for (YC(6)H(4))(3)P, a Hammett correlation of k(c) against 3sigma gives the reaction constant rho(c)(P) = +1.03, consistent with phosphine predissociation; for PyO rho(c)(N) = -3.84. It is so highly negative because PyO enters in three steps, each of which is improved by a better Lewis base or nucleophile, and again for (YC(6)H(4))(3)P as regards the k(4) step, rho(4) = -0.70, reflecting its role as a nucleophile in attacking a postulated dioxorhenium(VII) intermediate. The RCS is represented by the breaking of the covalent N-O bond within another intermediate inferred from the kinetics, [MeReO(mtp)(OPy)(2)], to yield the dioxorhenium(VII) species [MeRe(O)(2)(mtp)(OPy)]. A close analogue, [MeRe(O)(2)(mtp)Pic], was identified by (1)H NMR spectroscopy at 240 K in toluene-d(8). The role of the "second" PyO in the rate law and reaction scheme is attributed to its providing nucleophilic assistance to the RCS. Addition of an exogenous nucleophile (tetrabutylammonium bromide, Py, or Pic) caused an accelerating effect. When Pic was used, the rate law took on the new form v = k(NA)[1][PicO][Pic][PPh(3)](-1); k(NA) = 2.6 x 10(2) L mol(-1) s(-1) at 25.0 degrees C in benzene. The ratio k(c)/k(NA) is 58, consistent with the Lewis basicities and nucleophilicities of PicO and Pic.     

Synthesis and crystal structure of an unusual mixed crystal containing an oxorhenium(V) and imidorhenium(V) complex

An unusual mixed crystal of a square-pyramidal oxorhenium(V), [ReOCl(Hdua)], and an octahedral imidorhenium(V) complex, [Re(dua)Cl₂(PPh₃)], was prepared from the reaction of trans-[ReOCl₃(PPh₃)₂]_and (6Z)-6-(2-aminobenzylideneamino)- 5-amino-1,3-dimethylpyrimidine-2,4(1H,3H)-dione (H₃dua) in ethanol. Characterization was performed by single crystal X-ray structure determination and IR spectroscopy. The chelate Hdua is coordinated as a tridentate diamido-imine, and dua is chelated as an imido-imino-amide.     

Heterofunctionalized phosphines derived from (2-formylphenyl)diphenylphosphine and their reactions with oxorhenium(V) complexes

Reactions of [ReOCl₃(PPh₃)₂] with a potentially tridentate Schiff base derived from (2-formylphenyl)diphenylphosphine and 2-aminophenol, HL¹P, (HL¹P = Ph₂PC₆H₄-2-HCN(C₆H₄-2-OH)) result in a rapid decomposition of the Schiff base and the formation of a large number of hitherto non-identified metal-containing species, while from similar reactions with the analogoue phosphine oxide HL¹PO, (HL¹PO = Ph₂P(O)C₆H₄-2-HCN(C₆H₄-2-OH)) products of the compositions [ReOCl₂(PPh₃)(L¹PO)] (1) and [Re(NC₆H₄-2-OH)Cl₃(PPh₃)₂] (2) could be isolated. The structure of 2 is an experimental proof of the preceding, metal-induced cleavage of the C–N double bond. A subsequent reaction of the released 2-aminophenol forms the final phenylimido ligand.Reduction of HL¹P with NaBH₄ gives the phosphine amine H₂L²P (H₂L² = Ph₂P(C₆H₄-2-CH₂NH(C₆H₄-2-OH))) in good yield. Reactions of H₂L²P with common oxorhenium(V) complexes result in the formation of the stable rhenium(V) complex [ReOCl₂(HL²P)] (3) with a facially coordinated HL²P^? ligand.     

Synthesis and characterization of oxorhenium(v) diamido pyridine complexes that catalyze oxygen atom transfer reactions

The detailed syntheses of complexes 1-4, Re(O)(X)(DAP) (X = Me, 1; Cl, 2; I, 3; OTf (triflate), 4) incorporating the diamido pyridine (DAP) ancillary ligand (2,6-bis((mesitylamino)methyl)pyridine) are described and shown to be effective catalysts for oxygen atom transfer (OAT) reactions of PyO to PPh(3). The catalytic activities are as follows: 4≈3 > 2 > 1. The observed electronic trend is consistent with the turnover limiting reduction of the proposed Re(VII) dioxo intermediate, Re(O)(2)(X)(DAP), during the catalytic cycle. The catalytic activity of complexes 1-3 was compared to previously published diamido amine (DAAm) oxorhenium complexes of the type Re(O)(X)(DAAm) (X = Me, 5; Cl, 6; I, 7 and DAAm = N,N-bis(2-arylaminoethyl)methylamine) which exhibit hydrolytic degradation during the catalytic reaction. Complexes 1-3 displayed higher turnover frequencies compared to 5-7. This higher catalytic activity was attributed to the more rigid DAP ligand backbone, which makes the complexes less susceptible to decomposition. However, another decomposition pathway was proposed for this catalytic system due to the observation of Re(O)(3)((MesNCH(2))(MesNCH)NC(5)H(3)) 8 in which one arm of the DAP ligand is oxidized.     

Cooperation between metal and ligand in oxygen atom transport by N-confused porphyrin oxorhenium(V) complexes

N-Confused porphyrin oxorhenium(V) complexes were prepared and their X-ray structures were elucidated. The oxorhenium(V) complexes can transfer oxygen atom from pyridine N-oxide to triphenylphosphine, in which unique cooperation between metal and ligand was observed.     

Oxygen atom transfer reactivity from a dioxo-Mo(VI) complex to tertiary phosphines: synthesis, characterization, and structure of phosphoryl intermediate complexes

The oxygen atom transfer (OAT) reactivity of TpMoO2Cl with PMe3, PEt3, and PPhMe2 (where Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate) has been investigated. The OAT reactions proceed through a diamagnetic Mo(IV) phosphoryl intermediate complex of general formula TpMoOCl(OPR3) (OPR3 = OPMe3, OPEt3, OPPhMe2), which have been isolated and characterized by 1H and 31P NMR, UV-visible, and infrared spectroscopies and electrospray ionization mass spectrometry. Solid-state crystal structures of TpMoOCl(OPMe3) and TpMoOCl(OPPhMe2) are also reported, the oxygen-to-phosphorus distances agree with a double-bond formulation and a single bond between the metal and the phosphoryl oxygen atom. The stability of the phosphoryl intermediate complexes depends on the steric properties of the coordinated phosphine-oxides. These intermediate complexes have been converted to solvent-coordinated species, TpMoOCl(solv) (solv = acetonitrile or dmf), and the coordinated solvents exchange with the bulk solvent.     

O atom transfer from nitric oxide catalyzed by Fe(TPP).

The reaction of NO-Fe(TPP) with low pressures of NO gas proceeds through three distinct transformations, the first of which we suggest is the formation of an N--N-coupled, (NO)(2) adduct intermediate. The subsequent formation of NO(NO(2))Fe(TPP), which under these conditions readily loses NO, suggests that it is formed by addition of free NO(2) to the starting nitrosyl. A mechanism is proposed which implies that the addition of a competitive O atom acceptor would lead to catalytic production of N(2)O. In agreement with the proposed mechanism, the formation of N(2)O is decoupled from the formation of the nitrite by using PPh(3) as the competitive acceptor. The mechanism of O atom transfer was examined by cross-labeling experiments, which show that both O atoms in the intermediate are equivalent, even under catalytic conditions. The formation of an intermediate was confirmed by IR spectroscopy of the heterogeneous reaction of an NO-Fe(TPP) film with gaseous NO, in which transient, isotope-sensitive nu(NO) bands are seen prior to NO(NO(2))Fe(TPP) formation. Mixed (14)N/(15)N label experiments demonstrate coupling between the two bound nitrosyls in the transient species.     

Voltammetry of oxorhenium(V) complexes containing the [O=Re−OR] core and substituted pyridine ligands

Compounds of the general formula [ORe(OR)Cl₂(PPh₃)₂] and [ORe(OEt)Cl₂(PPh₃)(py)], where R=alkyl or aryl and py=a substituted pyridine, were synthesized and their voltammetric behaviour investigated. For the former, the electron-transfer mechanism was observed to be dependent on solvent. In dry MeCN, a quasi-reversible oxidation and a reduction followed by a chemical reaction was observed. There were indications of nucleophilic attack on electrochemically generated [ORe(OEt)Cl₂(PPh₃)₂]⁺, forming an unstable species whose reduction potentials were strongly dependent on the identity of the nucleophile. Voltammetric and spectroscopic observations of the oxorhenium(V) alkoxypyridine complex indicate the pyridine to be labile in halogenated hydrocarbon solvents but not in Me₂CO, MeCN, or CCl₄. Electrochemical generation of [ORe(OEt)Cl₂(PPh₃)(Cl_xC_yH_z)]⁺ (x=1,2, or 3; y=1 or 2; z=2,3, or 4) appears to be followed by transfer of a hydrogen atom from the solvent to form [(HO)Re(OEt)Cl₂(PPh₃)]⁺. Various pyridine complexes of this type were preparedvia substitution reactions under mild conditions. Varying the reaction conditions allowed the synthesis oftrans-dioxotetrapyridyl complexes in excellent yield.     

Oxygen atom transfer reactions from isolated (oxo)manganese(V) corroles to sulfides

A series of five free-base corroles were metalated and brominated to form 10 manganese(III) corroles. Two of the free-base corroles and six manganese(III) corroles were analyzed by X-ray crystallography, including one complex that may be considered a transition-state analogue of oxygen atom transfer (OAT) from (oxo)manganese(V) to thioansisole. Oxidation by ozone allowed for isolation of the 10 corresponding (oxo)manganese(V) corroles, whose characterization by (1)H and (19)F NMR spectroscopy and electrochemistry revealed a low-spin and triply bound manganese-oxygen moiety. Mechanistic insight was obtained by investigating their reactivity regarding stoichiometric OAT to a series of p-thioanisoles, revealing a magnitude difference on the order of 5 between the β-pyrrole brominated (oxo)manganese(V) corroles relative to the nonbrominated analogues. The main conclusion is that the (oxo)manganese(V) corroles are legitimate OAT agents under conditions where proposed oxidant-coordinated reaction intermediates are irrelevant. Large negative Hammett ρ constants are obtained for the more reactive (oxo)manganese(V) corroles, consistent with expectation for such electrophilic species. The least reactive complexes display very little selectivity to the electron-richness of the sulfides, as well as a non-first-order dependence on the concentration of (oxo)manganese(V) corrole. This suggests that disproportionation of the original (oxo)manganese(V) corrole to (oxo)manganese(IV) and (oxo)manganese(VI) corroles, followed by substrate oxidation by the latter complex, gains importance when the direct OAT process becomes progressively less favorable.     

A non-radical chain mechanism for oxygen atom transfer with a thiorhenium(V) catalyst

The compound MeRe(S)(mtp)(PPh3), 2, where mtpH2 is 2-(mercaptomethyl)thiophenol, was used to catalyze the reaction between pyridine N-oxides, PyO, and triphenylphosphine. The rate law is -d[PyO]/dt=kc'[2].[PyO](1/2), with kc' at 25.0 degrees C in benzene=0.68 (4-picoline N-oxide) and 3.5x10(-3) dm(3/2) mol(-1/2) s(-1) (4-NO2-pyridine N-oxide). A chain mechanism with three steady-state thiorhenium species as chain carriers is implicated.     

Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15-tris（pentafluorophenyl）corrole Mn（V）-oxo (F₁₅CMn（V）-oxo),5,15-bis（pentafluorophenyl）-10-（phenyl）corrole Mn（V）-oxo(F₁₀CMn（V）-oxo),5,15- bis（phenyl）-10-（pentafluorophenyl）corrole Mn（V）-oxo（F₅CMn（V）-oxo） and 5,10,15-tris（phenyl）corrole Mn（V）-oxo（F₀CMn（V）-oxo） with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn（V）-oxo corrole and alkene is solvent-dependent.     

Rhenium chemistry of azooximes: oxygen atom transfer, azoimine chelation, and imine-oxime contrast

The concerned azooximes (L1OH, 1) are of type p-X-C6H4C(N2Ph)(NOH) (X = H, Me, Cl). The reaction of [Re(MeCN)Cl3(PPh3)2] with [Ag(L1OH)(L1O)] in cold dichloromethane-acetonitrile solvent has furnished the green colored ionized azoimine complex [ReV(O)Cl(PPh3)2(L1)](PF6), 2. In effect L1O- has undergone oxidative addition, the oxygen atom being transferred to the metal site. Upon treatment of [ReV(NPh)Cl3(PPh3)2] with L1OH in solution, the neutral azoimine complex [ReV(NPh)Cl3(L1H)], 3, resulted due to the spontaneous transfer of the oxime oxygen atom to a PPh3 ligand, which is eliminated as OPPh3. In contrast, the oxime of 2-acetylpyridine (L2OH, 4) did not undergo oxygen atom transfer and simply afforded the imine-oxime complex [ReV(NC6H4Y)Cl2(PPh3)(L2O)], 5, upon reacting with [ReV(NC6H4Y)Cl3(PPh3)2] (Y = H, Me, Cl). The spectral and electrochemical properties of 2, 3, and 5 and the structures of three representative compounds are reported. In the cation of 2 (X = H) the two PPh3 ligands lie trans to each other and the equatorial plane is defined by the five-membered azoimine chelate ring and the oxo and chloro ligands. The oxo ligand which forms a model triple bond (Re-O length 1.616(6) A) lies cis to the imine-N atom. In 3 (X = Cl) the ReCl3 fragment has meridional geometry and the imido nitrogen lies trans to the imine nitrogen of the planar azoimine chelate ring. In 5 x H2O (Y = Me), the Cl, oximato-N, and P atoms define an equatorial plane and the pyridine-N lies trans to the imido-N. The water of crystallization is hydrogen bonded to the oximato oxygen atom (O...O, 2.829(5) A). Reaction models in which chelation of the azooxime precedes oxygen atom transfer are proposed on the basis of oxophilicity of trivalent rhenium, Lewis acid activity of pentavalent rhenium, electron withdrawal by the azo group, and observed relative disposition of ligands in products.     

Thermodynamic, kinetic, and mechanistic study of oxygen atom transfer from mesityl nitrile oxide to phosphines and to a terminal metal phosphido complex

The enthalpies of oxygen atom transfer (OAT) from mesityl nitrile oxide (MesCNO) to Me(3)P, Cy(3)P, Ph(3)P, and the complex (Ar[(t)Bu]N)(3)MoP (Ar = 3,5-C(6)H(3)Me(2)) have been measured by solution calorimetry yielding the following P-O bond dissociation enthalpy estimates in toluene solution (±3 kcal mol(-1)): Me(3)PO [138.5], Cy(3)PO [137.6], Ph(3)PO [132.2], (Ar[(t)Bu]N)(3)MoPO [108.9]. The data for (Ar[(t)Bu]N)(3)MoPO yield an estimate of 60.2 kcal mol(-1) for dissociation of PO from (Ar[(t)Bu]N)(3)MoPO. The mechanism of OAT from MesCNO to R(3)P and (Ar[(t)Bu]N)(3)MoP has been investigated by UV-vis and FTIR kinetic studies as well as computationally. Reactivity of R(3)P and (Ar[(t)Bu]N)(3)MoP with MesCNO is proposed to occur by nucleophilic attack by the lone pair of electrons on the phosphine or phosphide to the electrophilic C atom of MesCNO forming an adduct rather than direct attack at the terminal O. This mechanism is supported by computational studies. In addition, reaction of the N-heterocyclic carbene SIPr (SIPr = 1,3-bis(diisopropyl)phenylimidazolin-2-ylidene) with MesCNO results in formation of a stable adduct in which the lone pair of the carbene attacks the C atom of MesCNO. The crystal structure of the blue SIPr·MesCNO adduct is reported, and resembles one of the computed structures for attack of the lone pair of electrons of Me(3)P on the C atom of MesCNO. Furthermore, this adduct in which the electrophilic C atom of MesCNO is blocked by coordination to the NHC does not undergo OAT with R(3)P. However, it does undergo rapid OAT with coordinatively unsaturated metal complexes such as (Ar[(t)Bu]N)(3)V since these proceed by attack of the unblocked terminal O site of the SIPr·MesCNO adduct rather than at the blocked C site. OAT from MesCNO to pyridine, tetrahydrothiophene, and (Ar[(t)Bu]N)(3)MoN was found not to proceed in spite of thermochemical favorability.     

A mechanistic study of oxygen atom transfer from N-sulfonyloxaziridine to enolates

Enolate additions to chiral N-sulfonyloxaziridines providing enantiomerically enriched α-hydroxy carbonyl compounds is a reaction of importance, yet a clear understanding of the factors governing stereoinduction in these transformations remains ambiguous. This is despite, previous computational studies, one by Bach et al. employing truncated model systems exploring oxygen atom transfer to an unsubstituted lithium enolate and another by our own group. In clarifying this reactivity we report here a computational study examining oxygen atom transfer from 1-S-(+)-(10-camphorsulfonyl)oxaziridine, viz., archetypal Davis chiral oxaziridine to substituted Li, Na, K enolates offering improved mechanistic understanding. From this investigation, a revised model is offered revealing the metal cation, chelation effects and sterics as decisive stereocontrolling factors in enolate additions to chiral N-sulfonyloxaziridines affording enantiomerically enriched α-hydroxy carbonyl compounds.     

Nonclassical oxygen atom transfer reactions of oxomolybdenum(VI) bis(catecholate)

Mechanistic studies indicate that the oxomolybdenum(vi) bis(3,5-di-tert-butylcatecholate) fragment deoxygenates pyridine-N-oxides in a reaction where the oxygen is delivered to molybdenum but the electrons for substrate reduction are drawn from the bound catecholate ligands, forming 3,5-di-tert-butyl-1,2-benzoquinone.     

A density functional study of oxygen atom transfer reactions between biological oxygen atom donors and molybdenum(IV) bis(dithiolene) complexes

Density functional calculations have been used to investigate oxygen atom transfer reactions from the biological oxygen atom donors trimethylamine N-oxide (Me(3)NO) and dimethyl sulfoxide (DMSO) to the molybdenum(IV) complexes [MoO(mnt)(2)](2-) and [Mo(OCH(3))(mnt)(2)](-) (mnt = maleonitrile-1,2-dithiolate), which may serve as models for mononuclear molybdenum enzymes of the DMSO reductase family. The reaction between [MoO(mnt)(2)](2-) and trimethylamine N-oxide was found to have an activation energy of 72 kJ/mol and proceed via a transition state (TS) with distorted octahedral geometry, where the Me(3)NO is bound through the oxygen to the molybdenum atom and the N-O bond is considerably weakened. The computational modeling of the reactions between dimethyl sulfoxide (DMSO) and [MoO(mnt)(2)](2-) or [Mo(OCH(3))(mnt)(2)](-) indicated that the former is energetically unfavorable while the latter was found to be favorable. The addition of a methyl group to [MoO(mnt)(2)](2-) to form the corresponding des-oxo complex not only lowers the relative energy of the products but also lowers the activation energy. In addition, the reaction with [Mo(OCH(3))(mnt)(2)](-) proceeds via a TS with trigonal prismatic geometry instead of the distorted octahedral TS geometry modeled for the reaction between [MoO(mnt)(2)](2-) and Me(3)NO.